Separator for nonaqueous secondary battery, method for producing the same, and nonaqueous  secondary battery

ABSTRACT

The present invention is to provide a separator that is excellent in heat resistance, shutdown function, flame retardancy and handling property. The separator for a nonaqueous secondary battery of the invention is a separator for a nonaqueous secondary battery that has a polyolefin microporous membrane at least one surface of which is laminated with a heat resistant porous layer containing a heat resistant resin, and is characterized by containing an inorganic filler containing a metallic hydroxide that undergoes dehydration reaction at a temperature of 200 to 400° C.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a continuation of application Ser. No. 12/665,179 filed Dec. 17,2009, which is a 371 of PCT/JP2008/060862 filed Jun. 13, 2008, thedisclosure of which is incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a separator for a nonaqueous secondarybattery, and in particular, relates to a technique for enhancing safetyof a nonaqueous secondary battery.

BACKGROUND ART

A nonaqueous secondary battery, which is represented by a lithium ionsecondary battery, has a high energy density and is widely used as amain electric power source of a portable electronic equipment, such as aportable phone and a notebook computer. The lithium ion secondarybattery is demanded to attain a further high energy density, but has atechnical issue on assuring safety.

A separator plays an important role on assuring safety of a lithium ionsecondary battery, and under the current situation, a polyethylenemicroporous membrane is used since it has a high strength and shutdownfunction. The shutdown function referred herein means a function ofshutting down an electric current by closing the pores of themicroporous membrane when the temperature of the battery is increased,and the battery is suppressed from generating heat by the function,thereby preventing the battery from suffering thermal runaway.

The energy density of the lithium ion secondary battery is beingincreased year by year, and for assuring safety, heat resistance isdemanded in addition to the shutdown function. However, the shutdownfunction contradicts the heat resistance since the operation mechanismthereof depends on closure of the pores through melting of polyethylene.There have been proposals on improvement in heat resistance with themolecular weight of polyethylene, the crystalline structure or the like,but sufficient heat resistance has not yet been attained. Suchtechniques have been proposed that polypropylene is blended orlaminated, but under the current situation, these systems fail to attainsufficient heat resistance. Furthermore, for enhancing the heatresistance with the shutdown function attained simultaneously, suchtechniques have been proposed that heat resistant porous layers arecoated on both front and back surfaces of a polyethylene microporousmembrane, and nonwoven fabrics containing heat resistant fibers arelaminated thereon.

It is an important factor of a separator for assuring safety of anonaqueous secondary battery that the separator has shutdown functionand heat resistance, and furthermore, it is also important that theseparator has flame retardancy from the standpoint of ignition. Thecurrently available separator for a nonaqueous secondary battery asdescribed above uses a polyethylene microporous membrane inconsideration of shutdown characteristics, and there are many techniquesfor enhancing heat resistance mainly with the polyethylene microporousmembrane. Polyethylene is a polymer that is highly combustible, and inconsideration of the property, cannot be considered as having highsafety.

Such a separator has been known that has a polyethylene microporousmembrane and a heat resistant porous layer having an oxygen index of 26or more, which are laminated on each other (see Patent Document 1).However, a polyethylene microporous membrane is still combustible eventhough it is coated with a layer having a high oxygen index, and it isnot effective from the standpoint of flame retardancy.

Such a separator has been also known that has a polyethylene microporousmembrane and a heat resistant porous layer laminated on each other, inwhich ceramic powder is mixed in the heat resistant porous layer (seePatent Document 2). In Patent Document 2, the ceramic powder is mixedfor the purpose of improving the ion permeability. However, there is noeffect in flame retardancy by adding ceramic powder, which isrepresented by a so-called metallic oxide. Furthermore, the separatorhas a handling problem, in which an equipment is severely abraded due tothe ceramic particles, which are generally hard. In the case where theequipment is abraded, metallic powder and the like are attached to theseparator and may cause decrease in capability of the battery.

In addition, techniques for imparting flame retardant effect to theseparator by adding a flame retarder thereto (see Patent Documents 3 to6). Patent Document 3 discloses examples of utilizing a halogen flameretarder and barium sulfate in the form of solid particles. PatentDocuments 4 to 6 disclose examples of adding a polymer flame retarder toa separator. The proposals contribute to flame retardancy of aseparator, but cannot enhance the heat resistance sufficiently, and thusit is difficult to assure safety of a battery.

-   Patent Document 1: JP-A-2006-269359-   Patent Document 2: Japanese Patent No. 3,175,730-   Patent Document 3: JP-A-7-272762-   Patent Document 4: JP-A-2006-351316-   Patent Document 5: JP-A-2005-149881-   Patent Document 6: JP-A-2001-210314

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

It is the current situation that a practically useful separator thatattains such functions as heat resistance, shutdown function and flameretardancy and suffers no problem in handling property has not yet beenobtained. Accordingly, an object of the invention is to provide aseparator that is excellent in heat resistance, shutdown function, flameretardancy and handling property.

Means for Solving the Problems

The invention provides the following inventions for solving theproblems.

(1) A separator for a nonaqueous secondary battery containing apolyolefin microporous membrane at least one surface of which islaminated with a heat resistant porous layer containing a heat resistantresin, characterized by containing an inorganic filler containing ametallic hydroxide that undergoes dehydration reaction at a temperatureof 200 to 400° C.

(2) The separator for a nonaqueous secondary battery according to theitem (1), characterized in that the metallic hydroxide is at least oneof aluminum hydroxide and magnesium hydroxide.

(3) The separator for a nonaqueous secondary battery according to theitem (2), characterized in that the metallic hydroxide is aluminumhydroxide.

(4) The separator for a nonaqueous secondary battery according to one ofthe items (1) to (3), characterized in that the inorganic filler has anaverage particle diameter of 0.1 to 1 μm.

(5) The separator for a nonaqueous secondary battery according to one ofthe items (1) to (4), characterized in that the inorganic filler iscontained in the heat resistant porous layer.

(6) The separator for a nonaqueous secondary battery according to theitem (5), characterized in that the heat resistant porous layer containsthe inorganic filler in an amount of 50 to 95% by weight.

(7) The separator for a nonaqueous secondary battery according to one ofthe items (1) to (6), characterized in that the heat resistant resin isat least one of wholly aromatic polyamide, polyimide, polyamideimide,polysulfone, polyketone, polyetherketone, polyetherimide and cellulose.

(8) The separator for a nonaqueous secondary battery according to theitem (7), characterized in that the heat resistant resin is meta-typewholly aromatic polyamide.

(9) The separator for a nonaqueous secondary battery according to one ofthe items (1) to (8), characterized in that the separator for anonaqueous secondary battery has a thickness of 25 μm or less, thepolyethylene microporous membrane has a thickness of 5 μm or more, andthe heat resistant porous layer has a thickness of 2 μm or more.

(10) The separator for a nonaqueous secondary battery according to oneof the items (1) to (9), characterized in that the heat resistant porouslayer has a porosity of 60 to 90%.

(11) The separator for a nonaqueous secondary battery according to oneof the items (1) to (10), characterized in that the heat resistantporous layer is coated on both surfaces of the polyethylene microporousmembrane.

(12) The separator for a nonaqueous secondary battery according to oneof the items (1) to (11), characterized in that the heat resistant resinhas a molecular weight distribution Mw/Mn of 5≦Mw/Mn≦100 and a weightaverage molecular weight of 8.0×10³ to 1.0×10⁶.

(13) The separator for a nonaqueous secondary battery according to oneof the items (1) to (12), characterized in that the heat resistant resincontains a low molecular weight polymer having a molecular weight of8,000 or less in an amount of 1 to 15% by weight.

(14) The separator for a nonaqueous secondary battery according to theitem (7), characterized in that the heat resistant resin is whollyaromatic polyamide, and the wholly aromatic polyamide has an end groupconcentration ratio of [COOX]/[NH₂]≧1 (wherein X represents an alkalimetal or an alkaline earth metal).

(15) The separator for a nonaqueous secondary battery according to oneof the items (1) to (14), characterized in that the inorganic fillersatisfies the following items (a) and (b):

0.1≦d50≦1(μm)  (a)

0<α≦2  (b)

wherein d50 represents an average particle diameter (μm) of weightaccumulation of 50% by weight calculated from a smaller particle side ina particle size distribution by laser diffraction, and α representshomogeneity of the inorganic filler and is expressed by α=(d90−d10)/d50,wherein d90 represents an average particle diameter (μm) of weightaccumulation of 90% by weight calculated from a smaller particle side ina particle size distribution by laser diffraction, and d10 represents anaverage particle diameter (μm) of weight accumulation of 10% by weightcalculated from a smaller particle side in a particle size distributionby laser diffraction.

(16) A method for producing a separator for a nonaqueous secondarybattery containing a polyolefin microporous membrane at least onesurface of which is laminated with a heat resistant porous layercontaining a heat resistant resin, characterized by performing:

(i) a step of dissolving the heat resistant resin in a solvent, anddispersing therein an inorganic filler containing a metallic hydroxidethat undergoes dehydration reaction at a temperature of 200 to 400° C.to produce a coating slurry;

(ii) coating the slurry on at least one surface of the polyolefinmicroporous membrane;

(iii) immersing the polyolefin microporous membrane coated with theslurry in a coagulation liquid capable of coagulating the heat resistantresin;

(iv) removing the coagulation liquid by rinsing with water; and

(v) drying water.

(17) A nonaqueous secondary battery containing a positive electrode, anegative electrode, a separator provided between the electrodes, and anonaqueous electrolytic solution, characterized in that the separator isthe separator for a nonaqueous secondary battery according to one of theitems (1) to (15).

ADVANTAGES OF THE INVENTION

According to the invention, such a novel separator for a nonaqueoussecondary battery is obtained that is excellent in heat resistance,shutdown function, flame retardancy and handling property. The separatoris significantly advantageous for enhancing safety and durability of anonaqueous secondary battery.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 The figure is a graph showing evaluation results of shutdowncharacteristics of separators of the invention and other separators.

FIG. 2 The figure is a graph showing results of durability evaluation 1of separators of the invention and other separators.

FIG. 3 The figure is a graph showing results of durability evaluation 2of separators of the invention and other separators.

FIG. 4 The figure is a graph showing results of an oven test ofseparators of the invention and other separators.

FIG. 5 The figure is a graph showing results of DSC analysis ofseparators of the invention.

FIG. 6 The figure is a conceptual diagram showing schematically a GPCcurve.

BEST MODE FOR CARRYING OUT THE INVENTION

The separator for a nonaqueous secondary battery is a separator for anonaqueous secondary battery that contains a polyolefin microporousmembrane at least one surface of which is laminated with a heatresistant porous layer containing a heat resistant resin, and ischaracterized by containing an inorganic filler containing a metallichydroxide that undergoes dehydration reaction at a temperature of 200 to400° C.

One of the major characteristic features of the invention is the use ofa metallic hydroxide that undergoes dehydration reaction at atemperature of 200 to 400° C. as the inorganic filler. The use of themetallic hydroxide achieves flame retardancy of the separator for anonaqueous secondary battery and considerably enhances the safety of thebattery totally. It has been considered that in a separator for alithium ion secondary battery, the addition of an inorganic filleradversely influences the battery characteristics when a polar group,such as a hydroxyl group, is contained in the inorganic filler, andtherefore, a skilled person in this field of art has not selected ametallic hydroxide as a material used (see WO 98/32184, p. 7, lines 12to 16, and the like). However, the inventors have found that theaddition of a metallic hydroxide, such as aluminum hydroxide, to aseparator not only does not adversely influence the batterycharacteristics, but also provides various advantages including flameretardancy, and thus the invention has been completed.

The effects obtained by the addition of a metallic hydroxide will bespecifically described. A metallic hydroxide undergoes dehydrationreaction upon heating, thereby forming an oxide and releasing water. Thedehydration reaction is reaction that is associated with largeendotherm. Accordingly, in the case where a separator containing ametallic hydroxide is installed in a battery, dehydration reactionassociated with release of water and endotherm occurs upon increasingthe temperature of the battery, thereby attaining flame retardancy ofthe separator. The combustible electrolytic solution is diluted withreleased water, and thus flame retardancy of the electrolytic solutionis attained in addition to the separator, which is effective forattaining flame retardancy of the battery totally. A metallic hydroxideis relatively soft as compared to a metallic oxide, such as alumina, andthus does not cause a handling problem, such as abrasion of members usedin the steps upon production due to the inorganic filler contained inthe separator.

In the invention, the metallic hydroxide undergoes dehydration reactionat a temperature of 200 to 400° C., and preferably 250 to 350° C. It isconsidered that the most dangerous factor in a nonaqueous secondarybattery is endotherm associated with decomposition reaction at apositive electrode, and the decomposition reaction occurs around 300° C.Accordingly, endotherm of a battery can be effectively prevented fromoccurring when the temperature, at which dehydration reaction of themetallic hydroxide occurs, is in a range of 200 to 400° C. The negativeelectrode is safe when the temperature of the battery is 200° C. or moresince the negative electrode substantially loses activity to preventendothermic reaction with the generated water from occurring. When thedehydration temperature of the metallic hydroxide is 200° C. or more,the dehydration reaction does not occur at a temperature that is lowerthan the shutdown temperature of the polyolefin microporous membrane,and therefore, the shutdown characteristics are not influenced.

Examples of the metallic hydroxide include aluminum hydroxide, magnesiumhydroxide, calcium hydroxide, chromium hydroxide, nickel hydroxide,boron hydroxide and combinations of two or more of them, but theinvention is not limited to them. Among these, aluminum hydroxideundergoes dehydration reaction within a temperature range ofapproximately 250 to 300° C., and magnesium hydroxide undergoesdehydration reaction within a temperature range of approximately 350 to400° C. Accordingly, at least one of aluminum hydroxide and magnesiumhydroxide is preferably used in the invention. In particular, aluminumhydroxide is most preferred in consideration of effective use ofendotherm associated with the dehydration reaction. As the aluminumhydroxide, one having a gibbsite composition, one having a bayeritecomposition, and one having a mixed composition of them are preferred,and among these, one having a gibbsite composition is particularlypreferred. In addition to the inorganic filler containing a metallichydroxide, a metallic oxide, such as alumina, titania, silica andzirconia, and other inorganic fillers, such as a carbonate salt and aphosphate salt, may be used by mixing in such a range that the handlingproperty and the battery capability are not adversely affected.

Aluminum hydroxide is preferred as compared to the other metallichydroxides from the standpoint of shutdown characteristics and meltdowncharacteristics. Specifically, the inventors have evaluated a separatorcontaining aluminum hydroxide for shutdown characteristics, and havefound that the resistance is increased by approximately 10 times at atemperature around 100° C. (see Example 1 in FIG. 1). The phenomenonmeans that the separator of the invention starts shutdown at a lowertemperature than a conventional separator containing only a polyolefinmicroporous membrane or the like, and thus functions advantageously forassuring safety of a battery. The inventors have also found that theresistance of the battery is quickly increased when full-fledgedshutdown occurs by increasing the temperature of the battery to aroundthe melting point of polyethylene (see Example 1 in FIG. 1). Thephenomenon means that the separator of the invention can shut down anelectric current instantly when the temperature of the battery isincreased, and thus has excellent shutdown function. The behaviorefficiently functions when a thinner polyolefin microporous membrane isapplied to the base. The inventors have also found that the separator ofthe invention continuously maintains a high resistance value even in ahigh temperature region after shutdown (see Example 1 in FIG. 1). Thephenomenon means that the separator is excellent in anti-meltdowncharacteristics and is considerably excellent in safety at a hightemperature.

In addition, aluminum hydroxide and magnesium hydroxide are preferredsince they protect the positive electrode from hydrofluoric acid presentin the nonaqueous secondary battery to enhance the durability of thebattery. Specifically, in a nonaqueous secondary battery, hydrofluoricacid is a factor of corroding the positive electrode active substance todeteriorate the durability, but aluminum hydroxide and magnesiumhydroxide have a function of adsorbing and coprecipitating hydrofluoricacid. Accordingly, the use of a separator containing the metallichydroxide can maintain the hydrofluoric acid concentration in theelectrolytic solution to a low level, thereby enhancing the durabilityof the battery.

The separator of the invention may contain the inorganic filler in anyportion of the separator, for example, the polyolefin microporousmembrane, the heat resistant porous layer and other layers laminated onthese layers, and particularly preferably the inorganic filler iscontained in the heat resistant porous layer. In the separator of theinvention, the heat resistant porous layer imparts heat resistance tothe separator, and the addition of the inorganic filler to the layerfurther enhances the heat resistance of the heat resistant porous layer,thereby improving prevention of short circuit and dimensional stabilityat a high temperature. Furthermore, there is a general tendency that theheat resistant porous layer is electrostatically charged strongly, andowing to the phenomenon, is not favorable in handling property. In thecase where a metallic hydroxide, such as aluminum hydroxide, is added tothe heat resistant porous layer, the electric charge thus charged can berapidly attenuated. Accordingly, the electric charge can be maintainedto a low level, thereby enhancing the handling property of theseparator.

The average particle diameter of the inorganic filler containing themetallic hydroxide is preferably 0.1 to 1 μm. In the case where theaverage particle diameter exceeds 1 μm, the separator may unfavorablyfail to prevent sufficiently short circuit from occurring upon exposingthe separator to a high temperature. Furthermore, with the structure ofmixing the inorganic filler in the heat resistant porous layer, the heatresistant porous layer may be difficult to be formed to have a suitablethickness. In the case where the average particle diameter is less than0.1 μm, the inorganic filler is liable to be dropped off as powder fromthe separator, and thus in the case where the inorganic filler is mixedin the heat resistant porous layer, the strength of the heat resistantporous layer may be decreased. Furthermore, the use of a small filler issubstantially difficult from the standpoint of cost.

The inorganic filler preferably satisfies the following items (a) and(b).

0.1≦d50≦1(μm)  (a)

0<α≦2  (b)

More preferably, the above item (a) and the following item (c) aresatisfied.

0<α≦1  (c)

Herein, d50 represents an average particle diameter (μm) of weightaccumulation of 50% by weight calculated from a smaller particle side ina particle size distribution by laser diffraction. α representshomogeneity of the inorganic filler and is expressed by α=(d90−d10)/d50.d90 represents an average particle diameter (μm) of weight accumulationof 90% by weight calculated from a smaller particle side in a particlesize distribution by laser diffraction. d10 represents an averageparticle diameter (μm) of weight accumulation of 10% by weightcalculated from a smaller particle side in a particle size distributionby laser diffraction.

The use of the inorganic filler having the aforementioned particle sizedistribution increases the packing density of the inorganic filler inthe separator and enhances the effect of flame retardancy owing to theinorganic filler containing particles that have variation in particlediameter. Furthermore, the heat resistant porous layer is liable to befixed favorably to the polyolefin microporous membrane, therebypreventing the heat resistant porous layer from being dropped off.Moreover, the particles having a small diameter contribute to formationof pores in the heat resistant porous layer, and the particles having alarge diameter appear on the surface of the heat resistant porous layerto improve the sliding property. A value for d50 of less than 1 μm isnot preferred due to such factors that the inorganic filler is liable tobe dropped off as powder from the separator. A value for d50 exceeding 1μm is not preferred due to such factors that the heat resistant porouslayer is difficult to be formed to have a suitable thickness. When α is0, a monodisperse particle diameter is obtained to fail to provideenhancement of the packing density of the inorganic filler. When αexceeds 2, coarse particles or minute particles are contained, and thusthe coating property may be deteriorated.

The heat resistant porous layer of the invention contains the heatresistant resin, has numerous minute pores inside, and has such astructure that the minute pores are connected to each other, therebyproviding a porous layer, through which a gas or a liquid can pass fromone surface to the other surface.

As the heat resistant resin, a resin that has a melting point of 250° C.or more and a resin that does not substantially have a melting point buthas a thermal decomposition temperature of 250° C. or more arepreferably used. Examples of the heat resistant resin include at leastone selected from wholly aromatic polyamide, polyimide, polyamideimide,polysulfone, polyketone, polyetherketone, polyetherimide and cellulose.In particular, from the standpoint of durability, wholly aromaticpolyamide is preferably used, and meta-type wholly aromatic polyamide isfurther preferred from the standpoint that the porous layer can beeasily formed and is excellent in oxidation and reduction resistance.

The heat resistant resin preferably has a molecular weight distributionMw/Mn of 5≦Mw/Mn≦100 and a weight average molecular weight of 8.0×10³ to1.0×10⁶, thereby providing a favorable heat resistant porous layer uponforming the heat resistant porous layer by a wet coating method on thepolyolefin microporous membrane. Specifically, the heat resistant resinhaving a wide molecular weight distribution as shown above contains alarge amount of a low molecular weight matter, and a coating liquidcontaining the polymer dissolved therein is improved in processability.Accordingly, a heat resistant porous layer having less defects and ahomogeneous thickness can be easily provided. Furthermore, the coatingliquid can be coated favorably without application of a strong coatingpressure, whereby the surface pores of the polyolefin microporousmembrane are not clogged to prevent the air permeability at theinterface between the heat resistant porous layer and the polyolefinmicroporous membrane form being lowered. Moreover, when the coatingliquid is coated on the polyolefin microporous membrane and immersed ina coagulation liquid, the polymer in the coating liquid is enhanced inmobility to provide favorable pores. Further, the inorganic fillercontributing to the formation of pores can be prevented from beingdropped off as powder owing to good affinity between the low molecularweight matter and the inorganic filler. Consequently, a favorable heatresistant porous layer having uniform minute pores can be easilyprovided. Accordingly, such a separator can be obtained that hasexcellent ion permeability and good contact property with theelectrodes.

In a preferred embodiment, the heat resistant resin contains a lowmolecular weight polymer having a molecular weight of 8,000 or less inan amount of 1 to 15% by weight, and preferably in an amount of 3 to 10%by weight, whereby a favorable heat resistant porous layer can beprovided as similar to the above.

In the case where aromatic polyamide is used as the heat resistantresin, the aromatic polyamide has an end group concentration ratio of[COOX]/[NH₂]≧1. X represents hydrogen, an alkali metal or an alkalineearth metal. The end carboxyl group, such as COONa, has a function ofrenewing and removing an unfavorable film formed on the negativeelectrode of the battery. Accordingly, the use of aromatic polyamidehaving a larger amount of end carboxyl groups than end amine groupsprovides a nonaqueous secondary battery that has a stable dischargecapacity for a prolonged period of time. For example, such a battery canbe obtained that still has a favorable discharge capacity aftersubjecting to 100 charge-discharge cycles.

In the invention, the heat resistant porous layer preferably containsthe inorganic filler in an amount of 50 to 95% by weight, and morepreferably 70 to 85% by weight. When the weight fraction of theinorganic filler is less than 50% by weight, the characteristicsrelating to heat resistance, such as the dimensional stability at a hightemperature, may be insufficient. When it exceeds 95% by weight, thestrength of the heat resistant porous layer may be insufficient toprovide such problems as poor handling property due to drop-off ofpowder, and difficulty in molding.

The heat resistant porous layer preferably has a porosity of 60 to 90%.When the porosity of the heat resistant porous layer exceeds 90%, theheat resistance may be unfavorably insufficient. When it is less than60%, there is unfavorably such a tendency that the cyclecharacteristics, storage characteristics and discharge property aredeteriorated. The coated amount of the heat resistant porous layer ispreferably 2 to 10 g/m².

The polyolefin microporous membrane in the invention contains apolyolefin, has numerous minute pores inside, and has such a structurethat the minute pores are connected to each other, thereby providing amembrane, through which a gas or a liquid can pass from one surface tothe other surface. Examples of the polyolefin include polyethylene,polypropylene, polymethylpentene and combinations thereof. Polyethyleneis particularly preferred, and preferred examples of the polyethyleneinclude high density polyethylene and a mixture of high densitypolyethylene and ultrahigh molecular weight polyethylene.

The polyolefin microporous membrane preferably has a porosity of 20 to60%. When the porosity is less than 20%, the membrane resistance of theseparator is unfavorably increased, thereby decreasing the output powerof the battery. When the porosity exceeds 60%, the shutdowncharacteristics may be unfavorably decreased considerably.

The polyolefin microporous membrane preferably has an air permeabilityper unit thickness (JIS P8117) of 10 sec/100 cc·μm or more. When the airpermeability per unit thickness is lower than 10 sec/100 cc·μm, thepolyolefin microporous membrane may be unfavorably clogged at theinterface between the heat resistant porous layer and the polyolefinmicroporous membrane, thereby increasing the membrane resistancesignificantly and deteriorating the shutdown characteristicssignificantly.

The polyolefin microporous membrane preferably has Y/X of 1×10⁻³ to1×10⁻² ohm·cm²/(sec/100 cc), wherein the air permeability (JIS P8117) isrepresented by X sec/100 cc, and the membrane resistance uponimpregnating the polyolefin microporous membrane with an electrolyticsolution is represented by Y ohm·cm².

In general, the air permeability X is given by the following expression(1).

X=K(τ² ·L)/(ε·d)  (1)

wherein K represents a proportionality constant derived frommeasurement, τ represents the tortuosity, L represents the thickness,and d represents the average pore diameter. The membrane resistance Y isgiven by the following expression (2).

Y=ρ·τ ² ·L/ε  (2)

wherein ρ represents the specific resistance of the electrolyticsolution, with which the separator is impregnated. According to theexpressions (1) and (2), Y/X is given by the following expression (3).

Y/X=(ρ/K)·d  (3)

Accordingly, Y/X is a parameter that is proportional to the porediameter d of the polyolefin microporous membrane. The range of Y/X inthe invention is obtained by measuring the membrane resistance Y at 20°C. by using an electrolytic solution obtained by dissolving LiBF₄ in aconcentration of 1 M in a solvent containing propylene carbonate andethylene carbonate mixed at a weight ratio of 1/1. This means thefavorable range of the pore diameter d of the polyolefin microporousmembrane. A conventional polyolefin microporous membrane as a ordinaryseparator for a lithium ion secondary battery has Y/X in a range of1×10⁻² to 1×10⁻¹ ohm·cm²/(sec/100 cc), and the polyolefin microporousmembrane base in the invention has a small pore diameter as comparedthereto. The specific resistance ρ of the electrolytic solution at 20°C. is 2.66×10² ohm·cm, and K is 0.0778 sec/100 cc. Accordingly, ρ/K is3.4×10³ ohm·cm/(sec/100 cc). Consequently, the average pore diameter dis calculated to be 3.0 to 30 nm. When Y/X is less than 1×10⁻³ohm·cm²/(sec/100 cc), impregnation with an electrolytic solution may bedifficult to provide problems upon applying the separator. When Y/Xexceeds 1×10⁻² ohm·cm²/(sec/100 cc), clogging of the heat resistantporous layer may be induced at the interface between the heat resistantporous layer and the polyolefin microporous membrane, thereby providingsuch problems as increase of the membrane resistance of separator andsignificant deterioration of the shutdown characteristics.

In the invention, the heat resistant porous layer may be coated at leastone surface of the polyolefin microporous membrane serving as the base,and it is more preferred that it is coated on both surfaces thereof.This is because when it is coated on both surfaces thereof, not only aproblem due to curling can be avoided to improve the handling property,but also the dimensional stability at a high temperature can be largelyimproved, thereby enhancing the durability of the battery.

In the separator for a nonaqueous secondary battery of the invention,the polyolefin microporous membrane preferably has a thickness of 5 μmor more. When the thickness of the polyolefin microporous membrane isless than 5 μm, the mechanical properties thereof, such as the tensilestrength and the piercing strength, may be unfavorably insufficient. Theheat resistant porous layer preferably has a thickness of 2 μm or more.When the thickness of the heat resistant porous layer is less than 2 μm,it may be difficult to provide sufficient heat resistance. The separatorfor a nonaqueous secondary battery of the invention preferably has athickness of 25 μm or less, and more preferably 20 μm or less. When thethickness of the separator exceeds 25 μm, the energy density and theoutput characteristics of the battery, to which the separator isapplied, may be unfavorably decreased.

The separator for a nonaqueous secondary battery of the inventionpreferably has an air permeability (JIS P8117) of 500 sec/100 cc orless. When the air permeability exceeds 500 sec/100 cc, such a problemmay occur that the ion permeability becomes insufficient to increase themembrane resistance of the separator, which brings about decrease inoutput power of the battery. For providing an air permeability of 500sec/100 cc or less for the separator, the polyolefin microporousmembrane used therefor preferably has an air permeability of 400 sec/100cc or less.

The separator for a nonaqueous secondary battery of the inventionpreferably has a membrane resistance of 0.5 to 10 ohm·cm², and morepreferably 1 to 5 ohm·cm². The piercing strength thereof is preferably300 g or more, and more preferably 400 g or more. For the constitution,the polyolefin microporous membrane preferably has a piercing strengthof 300 g or more. The weight per unit varies largely depending on thespecific gravity of the constitutional materials and cannot bedetermined unconditionally, and it is preferably approximately 6 to 20g/m². The heat contraction ratio thereof is preferably 30% or less inboth MD and TD. The heat contraction ratio referred herein is a ratio ofdecrease in dimension of a specimen when the specimen is subjected to aheat treatment at 175° C. without tension. The oxygen index thereof ispreferably 19% or more. The half period of withstand voltage thereof ispreferably 30 minutes or less.

The method for producing the separator for a nonaqueous secondarybattery of the invention is not particularly limited, and the separatorcan be produced, for example, by the following steps:

(i) a step of dissolving the heat resistant resin in a solvent, anddispersing therein an inorganic filler containing a metallic hydroxidethat undergoes dehydration reaction at a temperature of 200 to 400° C.to produce a coating slurry;

(ii) coating the slurry on at least one surface of the polyolefinmicroporous membrane;

(iii) immersing the polyolefin microporous membrane coated with theslurry in a coagulation liquid capable of coagulating the heat resistantresin;

(iv) removing the coagulation liquid by rinsing with water; and

(v) drying water.

In the step (i), the solvent may be anyone that dissolves the heatresistant resin without particular limitation. Specifically, a polarsolvent is preferred, and examples thereof include N-methylpyrrolidone,dimethylacetamide, dimethylformamide and dimethylsulfoxide. The solventmay contain the polar solvent and additionally a poor solvent to theheat resistant resin, and the addition of the poor solvent induces amicroscopic phase separation structure to facilitate formation of poresupon providing the heat resistant porous layer. Preferred examples ofthe poor solvent include an alcohol, and a polyhydric alcohol, such asglycol, is particularly preferred. In the case where the dispersibilityof the inorganic filler is not good in the step (i), such a method maybe applied that the inorganic filler is surface-treated with a silanecoupling agent or the like to improve the dispersibility.

In the step (ii), the slurry is coated on at least one surface of thepolyolefin microporous membrane, and in the case where the heatresistant porous layers are formed on both surfaces of the polyolefinmicroporous membrane, it is preferred to coat the slurry on both thesurfaces of the polyolefin microporous membrane simultaneously from thestandpoint of reduction in steps. Examples of the method for coating theslurry include a knife coater method, a gravure coater method, a screenprinting method, a Meyer bar method, a die coater method, a reverse rollcoater method, an ink-jet method, a spraying method and a roll coatermethod. Among these, a reverse roll coater method is particularlypreferred from the standpoint that the coated film of the slurry systemis uniformly coated. In the case where the slurry is coated on both thesurfaces of the polyolefin microporous membrane, such a method may beexemplified that the polyolefin microporous membrane is passed between apair of Meyer bars to be coated with an excessive amount of the slurryon both surfaces, and then passed through a coater with a pair ofreverse rolls to scrape the excessive slurry, thereby precisely weighingthe slurry.

In the step (iii), the polyolefin microporous membrane coated with theslurry is immersed in a coagulation liquid capable of coagulating theheat resistant resin for coagulating the heat resistant resin, therebyforming a porous layer having the inorganic filler bound therein.Examples of the method include a method of spraying the coagulationliquid and a method of immersing in a bath containing the coagulationliquid (i.e., a coagulation bath). In the case where the coagulationbath is provided, it is preferably provided under the coating apparatus.

The coagulation liquid is not particularly limited as far as it cancoagulate the heat resistant resin, and from the standpoint of process,is preferably a mixture containing the solvent used in the slurry andwater added in a suitable amount. The amount of water mixed ispreferably 40 to 80% by weight. When the amount of water is less than40% by weight, such problems may occur that the period of time requiredfor coagulating the heat resistant resin is prolonged, and thecoagulation becomes insufficient. When the amount of water exceeds 80%by weight, such problems may occur that the cost is increased uponrecovering the solvent, and the surface in contact with the coagulationliquid is coagulated too quickly to prevent the surface from becomingporous sufficiently.

The step (iv) is a step of removing the coagulation liquid, and a methodof rinsing with water is preferred.

The step (v) is a step of drying water, and the drying method is notparticularly limited. The drying temperature is preferably 50 to 80° C.,and in the case where a high drying temperature is employed, a method ofmaking into contact with a roll is preferably employed for preventingdimensional change due to heat contraction from occurring.

The separator for a nonaqueous secondary battery of the invention may beapplied to a nonaqueous secondary battery of any mode that provides anelectromotive force through doping and dedoping of lithium. Thenonaqueous secondary battery of the invention has such structure that abattery element containing a negative electrode and a positive electrodefacing each other via a separator is impregnated with an electrolyticsolution, which are encapsulated in an outer package.

The negative electrode has such a structure that a negative electrodecomposition containing a negative electrode active substance, anelectroconductive assistant and a binder is formed on a collector.Examples of the negative electrode active substance include a materialcapable of electrochemically doping lithium, and specific examplesthereof include a carbon material, silicon, aluminum, tin and a wood'smetal. Examples of the electroconductive assistant include a carbonmaterial, such as acetylene black and Ketjen black. The binder containsan organic polymer, and examples thereof include polyvinylidene fluorideand carboxymethyl cellulose. As the collector, a copper foil, astainless steel foil, a nickel foil and the like may be used.

The positive electrode has such a structure that a positive electrodecomposition containing a positive electrode active substance, anelectroconductive assistant and a binder is formed on a collector.Examples of the positive electrode active substance include alithium-containing transition metal oxide, and specific examples thereofinclude LiCoO₂, LiNiO₂, LiMn_(0.5)Ni_(0.5)O₂,LiCo_(1/3)Ni_(1/3)Mn_(1/3)O₂, LiMn₂O₄ and LiFePO₄. Examples of theelectroconductive assistant include a carbon material, such as acetyleneblack and Ketjen black. The binder contains an organic polymer, andexamples thereof include polyvinylidene fluoride. As the collector, analuminum foil, a stainless steel foil, a titanium foil and the like maybe used.

The electrolytic solution has such a constitution that a lithium salt isdissolved in a nonaqueous solvent. Examples of the lithium salt includeLiPF₆, LiBF₄ and LiClO₄. Examples of the nonaqueous solvent includepropylene carbonate, ethylene carbonate, dimethyl carbonate, diethylcarbonate, ethylmethyl carbonate, γ-butyrolactone and vinylenecarbonate, which may be used solely or after mixing.

Examples of the outer package material include a metallic canister andan aluminum laminated package. The shape of the battery include arectangular shape, a cylinder shape, a coil shape and the like, to allof which the separator of the invention may be applied.

EXAMPLES 1. Measurement Methods

The measurement methods in the examples will be described.

[Average Particle Diameter and Particle Size Distribution of InorganicFiller]

The measurement was performed with a laser diffraction particle sizedistribution measuring apparatus (Mastersizer 2000, produced by SysmexCorporation). Water was used as a dispersion medium, and a minute amountof a nonionic surfactant (Triton X-100) was used as a dispersant. Thecenter particle diameter (D50) in the volume particle size distributionwas designated as the average particle diameter.

[Thickness]

The thickness was obtained by measuring 20 points per a specimen with acontact type thickness meter (produced by Mitutoyo Corporation), andobtaining the average value of them. The contact probe used had acylindrical shape with a diameter on the bottom surface of 0.5 cm, andthe measurement was performed under the condition where a load of 1.2kg/m² was applied to the contact probe.

[Air Permeability]

The air permeability (sec/100 cc) was measured according to JIS P8117.The air permeability per unit thickness was obtained by dividing themeasured air permeability (sec/100 cc) by the thickness (μm).

[Weight Per Unit]

A separator as a specimen was cut into a dimension of 10 cm×10 cm, whichwas measured for weight, and the measured value was converted to theweight per 1 m² to provide the weight per unit.

[Coated Amount of Heat Resistant Porous Layer]

The separator having the heat resistant porous layer coated thereon andthe polyethylene microporous membrane used therefor were measured forweight per unit, and the coated amount of the heat resistant porouslayer was obtained from the difference between them.

[Porosity]

The porosity ε (%) was obtained by the following expression:

ε={1−(Wa/da+Wb/db+Wc/dc+ . . . +Wn/dn)/t}×100

wherein a, b, c . . . n represent the constitutional materials; Wa, Wb,We . . . Wn represent the weights of the constitutional materials(g·cm²); da, db, dc . . . dn represent the true densities thereof(g/cm³); and t represents the thickness of the layer to be measured(cm).

[Membrane Resistance]

A separator as a specimen was cut into a dimension of 2.6 cm×2.0 cm. Thecut specimen was immersed in a methanol solution having 3% by weight ofa nonionic surfactant (Emulgen 210P, produced by Kao Corporation)dissolved therein, followed by air drying. An aluminum foil having athickness of 20 μm was cut into a dimension of 2.0 cm×1.4 cm, and wasattached with a conductive lead tab. Two pieces of the aluminum foilwere prepared, and the cut separator was held with two pieces of thealuminum foil, which were prevented from forming short circuit. Theseparator was impregnated with an electrolytic solution, which wasformed by dissolving LiBF₄ in a concentration of 1 M in a solventcontaining propylene carbonate and ethylene carbonate mixed at a weightratio of 1/1. The assembly was encapsulated in an aluminum laminatedpackage under reduced pressure with the tabs being outside the aluminumpackage. The cells were produced each with one piece, two pieces orthree pieces of the separator within the aluminum foil. The cells wereplaced in a thermostatic bath at 20° C., and the cells were measured forresistance by an alternating current impedance method with an amplitudeof 10 mV and a frequency of 100 kHz. The resistance values of the cellsthus measured were plotted against the number of pieces of theseparator, and the plots were linearly approximated to provide thegradient. The gradient was multiplied by the electrode area, i.e., 2.0cm×1.4 cm, to provide the membrane resistance (ohm·cm²) per one piece ofthe separator.

[Heat Contraction Ratio]

A separator as a specimen was cut into a dimension of 18 cm (MD)×6 cm(TD). Marks were attached to the positions (point A and point B) on theline bisecting the TD at 2 cm and 17 cm from the upper edge,respectively. Furthermore, marks were attached to the positions (point Cand point D) on the line bisecting the MD at 1 cm and 5 cm from the leftedge, respectively. A clip was attached to the specimen (the positionwhere the clip was attached was a position within the area of 2 cm inthe MD from the upper edge), which was hanged in an oven adjusted to175° C. for subjecting to a heat treatment for 30 minutes withouttension. The distances between the points A and B and between the pointsC and D were measured before and after the heat treatment, and the heatcontraction ratio was obtained by the expressions 4 and 5 below.

heat contraction ratio in MD={(distance AB before heattreatment−distance AB after heat treatment)/distance AB before heattreatment}×100  (4)

heat contraction ratio in TD={(distance CD before heattreatment−distance CD after heat treatment)/distance CD before heattreatment}×100  (5)

[Piercing Strength]

A separator as a specimen was subjected to a piercing test with a handycompression tester KES-G5, produced by Kato Tech Co., Ltd., underconditions of a curvature radius of the probe tip of 0.5 mm and apiercing speed of 2 mm/sec. The specimen was fixed by holding with ametallic frame having a hole with a diameter of 11.3 mm (specimenholder) along with silicone rubber packing. The maximum piercing load inthe test was designated as the piercing strength.

[Oxygen Index]

The oxygen index was measured with a combustibleness tester ON-1,produced by Suga Test Instruments Co., Ltd., according to JIS K7201. Ahigher oxygen index means excellent combustibleness.

[Sliding Property]

The sliding property was evaluated with a card friction tester, producedby Toyo Seiki Seisaku-sho, Ltd. Specifically, a separator as a specimenwas adhered to a weight of 1 kg (76 mm square), which was placed on aSUS stage with the separator directed downward. The weight was slid by10 cm at a velocity of 90 cm/min. The surface of the specimen, which hadbeen in contact with the SUS stage, was observed and confirmed as towhether or not it turned black. In the case where it turned black, itwas determined that SUS as the stage material was abraded, and thus thespecimen was evaluated as “poor”. In the case where it did not turnblack, it was determined that SUS as the stage material was not abraded,and thus the specimen was evaluated as “good”.

[Half Period of Withstand Voltage]

The half period of withstand voltage was measured with Honestmeter(Model HO110, produced by Shishido Electrostatic, Ltd.). The measurementenvironment was a temperature of 20° C. and a humidity of 50%. Aspecimen was fixed to a specimen holder and applied with a voltage underthe condition of a distance between the voltage application device andthe specimen of 20 mm and an applied voltage of 5 kV. After saturatingthe electric charge, the voltage attenuating behavior was confirmed for3 minutes, and the half period was calculated from the attenuationcurve. A separator having a shorter half period of withstand voltage canmaintain electric charge to a lower level and thus has favorablehandling property.

[Coating Property]

A separator as a specimen was wound into a roll form and stored at roomtemperature for one month. Thereafter, the separator was wound off, andthe surface state of the heat resistant porous layer was observed forevaluating the presence of missing portions of the heat resistant porouslayer. The case where no missing portion was observed was evaluated as“good”. The case where missing portions were observed was evaluated as“poor”.

[Molecular Weight and Molecular Weight Distribution]

1% by weight of a polymer was dissolved in a solution containing DMFhaving 0.01 mol/L of LiCl dissolved therein, and the solution as aspecimen was subjected to a GPC measurement to calculate a molecularweight distribution. The measurement was performed with ShimadzuChromatopac C-R4A and a GPC column (GPC KD-802, produced by Showa DenkoK.K.) at a detecting wavelength of 280 nm. Polystyrene molecular weightstandard substances were used as the reference. As for a separatorhaving composite of a polyethylene microporous membrane and an aramidporous layer, 1 g of the composite separator was sampled and added to 20g of DMF having 0.01 mol/L of LiCl dissolved therein, and only aramidwas dissolved at 80° C. to provide a measurement specimen. The content(% by weight) of the low molecular weight polymer in the heat resistantpolymer was obtained by dividing the value S1, which was obtained byintegrating the GPC curve in a zone of molecular weight of 0 to 8.0×10³,by the value S2, which was obtained by integrating the GPC curve in azone of molecular weight of 0 to 1.0×10⁶, and multiplying the resultingvalue by 100, as shown in FIG. 6. The molecular weight distribution(MWD) referred herein is expressed by the ratio of the weight averagemolecular weight (Mw) and the number average molecular weight (Mn)obtained by GPC, and is a value obtained by the expression (6) below.The weight average molecular weight (Mw) and the number averagemolecular weight (Mn) were obtained by calculating in the entire zone ofmolecular weight of 0 to 1.0×10⁶.

MWD=Mw/Mn  (6)

[End Group Concentration of Wholly Aromatic Polyamide]

A DMF solution containing 1% by weight of a polymer and 0.05% by weightof lithium chloride was used as a measurement specimen, which wasmeasured with Shimadzu Chromatopac C-R4A and an ODS (octadecylsilyl)column at a detecting wavelength of 280 nm. A polymer to be evaluatedwas a polymer immediately after production or was collected from a heatresistant layer incorporated in a composite separator. As a method formeasuring a molecular weight distribution of aramid from a heatresistant layer incorporated in a composite separator, 1 g of thecomposite separator was sampled and added to 20 g of DMF having 0.01mol/L of LiCl dissolved therein, and only aramid was dissolved at 80° C.to provide a measurement specimen.

2. Studies on Effect of Addition of Metallic Hydroxide

A separator of the invention and a comparative separator were prepared,and the effect of addition of an inorganic filler containing a metallichydroxide was studied.

Example 1

GUR2126 (weight average molecular weight: 4,150,000, melting point: 141°C.) and GURX143 (weight average molecular weight: 560,000, meltingpoint: 135° C.), produced by Ticona, were used as polyethylene powder.GUR2126 and GURX143 in a ratio of 1/9 (weight ratio) were dissolved in amixed solvent of liquid paraffin and decalin in a polyethyleneconcentration of 30% by weight to produce a polyethylene solution. Thepolyethylene solution had a composition of polyethylene/liquidparaffin/decalin=30/45/25 (weight ratio). The polyethylene solution wasextruded from a die at 148° C. and cooled in a water bath, followed bydrying at 60° C. for 8 minutes and 95° C. for 15 minutes, to produce agel tape (base tape). The base tape was stretched by biaxial stretchingwhere longitudinal stretching and transversal stretching were performedsequentially. The longitudinal stretching was 5.5 times at a stretchingtemperature of 90° C., and the transversal stretching was 11.0 times ata stretching temperature of 105° C. After the transversal stretching,thermal fixation was performed at 125° C. The base tape was thenimmersed in a methylene chloride bath to extract liquid paraffin anddecalin. Thereafter, the base tape was dried at 50° C. and subjected toan annealing process at 120° C. to provide a polyethylene microporousmembrane. The properties of the resulting polyethylene microporousmembrane were a thickness of 11.5 μm, a porosity of 36%, an airpermeability of 301 sec/100 cc, an air permeability per unit thicknessof 26 sec/100 cc·μm, a membrane resistance of 2.641 ohm·cm² and apiercing strength of 380 g. The value Y/X of the polyethylenemicroporous membrane obtained by dividing the membrane resistance by theair permeability was 8.77×10⁻³ ohm·cm²/(sec/100 cc).

Conex (a trade name, produced by Teijin Techno Products, Ltd.) asmeta-type wholly aromatic polyamide and aluminum hydroxide (H-43M,produced by Showa Denko K.K.) having an average particle diameter of 0.8μm were adjusted to a weight ratio of 25/75 and were mixed with a mixedsolvent containing dimethylacetamide (DMAc) and tripropylene glycol(TPG) at a weight ratio of 50/50 to a concentration of the meta-typewholly aromatic polyamide of 5.5% by weight, thereby producing a coatingslurry.

A pair of Meyer bars (size number #6) were disposed to face each otherwith a gap of 20 μm. An appropriate amount of the coating slurry wasplaced on the Meyer bars, and the polyethylene microporous membrane waspassed through the Meyer bars, thereby coating the coating slurry onboth the surfaces of the polyethylene microporous membrane. The membranewas immersed in a coagulation bath at a weight ratio of water/DMAc/TPGof 50/25/25 at 40° C., and then rinsed with water and dried to form aheat resistant porous layers on both the front and back surfaces of thepolyethylene microporous membrane, thereby producing a separator for anonaqueous secondary battery of the invention.

The properties of the separator were a weight per unit of 10.82 g/m², acoated amount of 3.83 g/m², a total thickness of 17.8 μm, a totalporosity of 48%, a porosity of the heat resistant porous layer of 71%,an air permeability of 360 sec/100 cc, a membrane resistance of 3.818ohm·cm², a heat contraction ratio in MD of 18.0%, a heat contractionratio in TD of 22.3%, a piercing strength of 405 g, an oxygen index of20.5%, favorable sliding property (“good”), and a half period ofwithstand voltage of 9.9 minutes.

Example 2

A separator for a nonaqueous secondary battery of the invention wasproduced in the same manner as in Example 1 except that the aluminumhydroxide was changed to magnesium hydroxide having an average particlediameter of 0.8 μm (Kisuma 5P, produced by Kyowa Chemical Industry Co.,Ltd.).

The properties of the separator were a weight per unit of 13.72 g/m², acoated amount of 6.73 g/m², a total thickness of 22.4 μm, a totalporosity of 52%, a porosity of the heat resistant porous layer of 69%,an air permeability of 368 sec/100 cc, a membrane resistance of 3.979ohm·cm², a heat contraction ratio in MD of 16.3%, a heat contractionratio in TD of 19.2%, a piercing strength of 406 g, an oxygen index of20.0%, favorable sliding property (“good”), and a half period ofwithstand voltage of 19.8 minutes.

Example 3

A separator for a nonaqueous secondary battery of the invention wasproduced in the same manner as in Example 1 except that the coatingslurry was supplied from one side of the pair of Meyer bars to form aheat resistant porous layer on one surface of the polyethylenemicroporous membrane.

The properties of the separator were a weight per unit of 10.62 g/m², acoated amount of 3.63 g/m², a total thickness of 20.0 μm, a totalporosity of 54%, a porosity of the heat resistant porous layer of 79%,an air permeability of 355 sec/100 cc, a membrane resistance of 3.879ohm·cm², a piercing strength of 402 g, an oxygen index of 20.0%,favorable sliding property (“good”), and a half period of withstandvoltage of 10.1 minutes when a voltage was applied to the side of theheat resistant porous layer and exceeding 30 minutes when a voltage wasapplied to the side of the polyethylene microporous membrane. Theseparator exhibited curling and was not favorable in handling property.The heat contraction ratios thereof were not able to be measured due tothe curling.

Comparative Example 1

The same polyethylene microporous membrane as in Example 1 was used.

Conex (a trade name, produced by Teijin Techno Products, Ltd.) asmeta-type wholly aromatic polyamide and alumina (AL160SG-3, produced byShowa Denko K.K.) having an average particle diameter of 0.6 μm wereadjusted to a weight ratio of 15/85 and were mixed with a mixed solventcontaining dimethylacetamide (DMAc) and tripropylene glycol (TPG) at aweight ratio of 50/50 to a concentration of the meta-type whollyaromatic polyamide of 5.5% by weight, thereby producing a coatingslurry.

A pair of Meyer bars (size number #6) were disposed to face each otherwith a gap of 20 μm. An appropriate amount of the coating slurry wasplaced on the Meyer bars, and the polyethylene microporous membrane waspassed through the Meyer bars, thereby coating the coating slurry onboth the surfaces of the polyethylene microporous membrane. The membranewas immersed in a coagulation bath at a weight ratio of water/DMAc/TPGof 50/25/25 at 40° C., and then rinsed with water and dried to form aheat resistant porous layers on both the front and back surfaces of thepolyethylene microporous membrane, thereby producing a separator for anonaqueous secondary battery of Comparative Example 1.

The properties of the separator were a weight per unit of 13.96 g/m², acoated amount of 6.97 g/m², a total thickness of 20.2 μm, a totalporosity of 51%, a porosity of the heat resistant porous layer of 74%,an air permeability of 366 sec/100 cc, a membrane resistance of 3.711ohm·cm², a heat contraction ratio in MD of 17.1%, a heat contractionratio in TD of 19.5%, and a piercing strength of 429 g. The separatorhad an oxygen index of 17.5, favorable sliding property (“good”), and ahalf period of withstand voltage exceeding 30 minutes. It is understoodfrom the above that Comparative Example 1 is inferior inflame retardancyand handling property as compared to Examples 1 to 3.

Comparative Example 2

The same polyethylene microporous membrane as in Example 1 was used.

Conex (a trade name, produced by Teijin Techno Products, Ltd.) asmeta-type wholly aromatic polyamide was mixed with a mixed solventcontaining dimethylacetamide (DMAc) and tripropylene glycol (TPG) at aweight ratio of 60/40 to a concentration of the meta-type whollyaromatic polyamide of 6.0% by weight, thereby producing a coating dope.

A pair of Meyer bars (size number #6) were disposed to face each otherwith a gap of 20 μm. An appropriate amount of the coating slurry wasplaced on the Meyer bars, and the polyethylene microporous membrane waspassed through the Meyer bars, thereby coating the coating dope on boththe surfaces of the polyethylene microporous membrane. The membrane wasimmersed in a coagulation bath at a weight ratio of water/DMAc/TPG of50/30/20 at 40° C., and then rinsed with water and dried to form a heatresistant porous layers on both the front and back surfaces of thepolyethylene microporous membrane, thereby producing a separator for anonaqueous secondary battery of Comparative Example 2.

The properties of the separator were a weight per unit of 9.24 g/m², acoated amount of 2.25 g/m², a total thickness of 17.7 μm, a totalporosity of 49%, a porosity of the heat resistant porous layer of 73%,an air permeability of 455 sec/100 cc, a membrane resistance of 3.907ohm·cm², a heat contraction ratio in MD of 24.4%, a heat contractionratio in TD of 56.8%, a piercing strength of 401 g, and unfavorablesliding property (“poor”). The separator had an oxygen index of 17.5%and a half period of withstand voltage exceeding 30 minutes. It isunderstood from the above that Comparative Example 2 is inferior in heatresistance, flame retardancy and handling property as compared toExamples 1 to 3.

Comparative Example 3

A commercially available polyethylene microporous membrane for aseparator for a nonaqueous secondary battery (E20MMS, produced by TonenCorporation) was used.

The properties of the polyethylene microporous membrane were a weightper unit of 12.9 g/m², a thickness of 20.0 μm, a porosity of 32%, an airpermeability of 543 sec/100 cc, an air permeability per unit thicknessof 27.2 sec/100 cc·μm, a membrane resistance of 5.828 ohm·cm², and apiercing strength of 496 g. The value Y/X of the polyethylenemicroporous membrane obtained by dividing the membrane resistance by theair permeability was 1.07×10⁻² ohm·cm²/(sec/100 cc). The separator wasnot able to be measured for heat contraction ratios due to significantmelting, and was difficult to be measured for oxygen index due tosignificant contraction. The half period of withstand voltage thereofexceeded 30 minutes. It is understood from the above that ComparativeExample 3 is significantly inferior in heat resistance, flame retardancyand handling property as compared to Examples 1 to 3.

[Evaluation of Properties of Separators]

The constitutions and properties of Examples 1 to 3 and ComparativeExamples 1 to 3 are summarized in Table 1. In Table 1, a half period ofwithstand voltage exceeding 30 minutes is expressed by “>30”.

TABLE 1 Comparative Comparative Comparative Example 1 Example 2 Example3 Example 1 Example 2 Example 3 Inorganic Kind Al(OH)₃ Mg(OH)₂ Al(OH)₃Al₂O₃ — — filler Average particle diameter (μm) 0.8 0.8 0.8 0.6 — —Content (% by weight) 75 75 75 85 — — Coated surface both both one bothboth — surfaces surfaces surface surfaces surfaces Weight per unit(g/m²) 10.82 13.72 10.62 13.96 9.24 12.9 Coated amount (g/m²) 3.83 6.733.63 6.97 2.25 — Thickness Separator 17.8 22.4 20.0 20.2 17.7 20.0 (μm)Polyethylene microporous membrane 11.5 11.5 11.5 11.5 11.5 20.0 Heatresistant porous layer 6.3 10.9 8.5 8.7 6.2 — Porosity Separator 48 5254 51 49 32   (%) Polyethylene microporous membrane 36 36 36 36 36 32  Heat resistant porous layer 71 69 79 74 73 — Air permeability (sec/100cc) 360 368 355 366 455 543   Membrane resistance (ohm · cm²) 3.8183.979 3.879 3.711 3.907   5.828 Heat MD 18.0 16.3 —⁽¹ 17.1 24.4   —⁽²contraction TD 22.3 19.2 —⁽¹ 19.5 56.8   —⁽² ratio (%) Piercing strength(g) 405 406 402 429 401 496   Oxygen index (%) 20.5 20.0 20.0 17.5 17.5  —⁽³ Sliding property good good good good poor good Half period ofwithstand voltage (min) 9.9 19.8 10.1⁽⁴ > 30⁽⁴ >30 >30 >30   ¹⁾Unable tomeasure due to curling ²⁾Unable to measure due to melting ³⁾Unable tomeasure due to significant contraction ⁴⁾Upper line: value on applyingvoltage to coated surface Lower line: value on applying voltage tosurface of polyethylene microporous membrane

[Evaluation of Shutdown (SD) Characteristics]

The separators of Examples 1 and 2 and Comparative Examples 1 and 3 asspecimens were each punched to a circle with a diameter of 19 mm, andimmersed in a methanol solution having 3% by weight of a nonionicsurfactant (Emulgen 210P, produced by Kao Corporation) dissolvedtherein, followed by air drying. The separator was impregnated with anelectrolytic solution and held by SUS plates (diameter: 15.5 mm). Theelectrolytic solution was obtained by dissolving LiBF₄ in aconcentration of 1 M in a solvent containing propylene carbonate andethylene carbonate mixed at a weight ratio of 1/1. The assembly wasencapsulated in a 2032 type coin cell. Lead wires were connected to thecoin cell, which was attached with a thermocouple and placed in an oven.The temperature was increased at a temperature increasing rate of 1.6°C./min, and the cell was applied with an alternating electric currenthaving an amplitude of 10 mV and a frequency of 1 kHz, thereby measuringthe resistance of the cell. The results of the measurement are shown inFIG. 1.

It is understood from FIG. 1 that Examples 1 and 2 show favorableshutdown characteristics as similar to the polyethylene microporousmembrane of Comparative Example 3, and shutdown starts to occur at alower temperature than Comparative Example 1. In particular, Example 1increases in resistance by approximately 10 times around 100° C., andthus is preferred from the standpoint that shutdown occurs at a lowertemperature.

In a temperature range of approximately 150° C. or more after shutdown,Examples 1 and 2 continuously maintain a high resistance while varyingslightly. On the other hand, the resistance of Comparative Example 1 isgradually decreased, and that of Comparative Example 3 is quicklydecreased. It is understood from the above that Examples 1 and 2 areexcellent in anti-meltdown characteristics as compared to ComparativeExamples 1 and 3. In particular, it is confirmed that Example 1 hasconsiderably excellent anti-meltdown characteristics.

[Test Production of Nonaqueous Secondary Battery]

89.5 parts by weight of powder of lithium cobaltate (LiCoO₂, produced byNippon Chemical Industrial Co., Ltd.), 4.5 parts by weight of acetyleneblack (Denka Black, a trade name, produced by Denki Kagaku Kogyo Co.,Ltd.) and 6 parts by weight of polyvinylidene fluoride (produced byKureha Corporation) were kneaded with N-methyl-2-pyrrolidone as asolvent to produce a slurry. The resulting slurry was coated on analuminum foil having a thickness of 20 μm, and dried, followed bypressing, to provide a positive electrode of 100 μm.

87 parts by weight of powder of mesophase carbon microbeads (MCMB,produced by Osaka Gas Chemicals Co., Ltd.), 3 parts by weight ofacetylene black (Denka Black, a trade name, produced by Denki KagakuKogyo Co., Ltd.) and 10 parts by weight of polyvinylidene fluoride(produced by Kureha Corporation) were kneaded withN-methyl-2-pyrrolidone as a solvent to produce a slurry. The resultingslurry was coated on a copper foil having a thickness of 18 μm, anddried, followed by pressing, to provide a negative electrode of 90 μm.

The positive electrode and the negative electrode were disposed to faceto each other with a separator intervening therebetween. The assemblywas impregnated with an electrolytic solution and encapsulated in anouter package formed of an aluminum laminated film to produce anonaqueous secondary battery. The electrolytic solution (produced byKishida Chemical Co., Ltd.) in which LiPF₆ was dissolved at aconcentration of 1 M in a solvent containing ethylene carbonate andethylmethyl carbonate mixed at a weight ratio of 3/7 was used.

The test-produced battery had a positive electrode area of 2×1.4 cm², anegative electrode area of 2.2×1.6 cm², and a capacity of 8 mAh (in arange of 4.2 V to 2.75 V).

[Evaluation of Durability 1]

Nonaqueous secondary batteries were produced according to theaforementioned manner by using the separator of Example 1 and thepolyethylene microporous membrane of Comparative Example 3. Thebatteries were each charged for 100 hours at 60° C., a constant currentof 8 mA and a constant voltage of 4.3 V. The time-lapse change of thecharging current is shown in FIG. 2.

After completing the test, the cell was disassembled, and the separatorwas observed. The polyethylene microporous membrane of ComparativeExample 3 was discolored to black, and the discoloration was conspicuouson the surface that was in contact with the positive electrode. On theother hand, no discoloration was found in the separator of Example 1.

It is understood from FIG. 2 and the observation results that Example 1is excellent in anti-redox property and has high durability as comparedto Comparative Example 3.

[Evaluation of Durability 2]

Nonaqueous secondary batteries were produced according to theaforementioned manner by using the separator of Example 1 and thepolyethylene microporous membrane of Comparative Example 3. Thebatteries were each charged at 60° C., a constant current of 8 mA and aconstant voltage of 4.3 V. The charging was terminated at an arbitrarytime, and at a battery voltage of 4.3 V and 25° C., the battery wasapplied with an alternating current of a frequency of 100 kHz and anamplitude of 10 mV to measure the alternating current resistance of thecell. The results are shown in FIG. 3.

The cell after completing the measurement was observed, and as a result,it was confirmed that the cell using the polyethylene microporousmembrane of Comparative Example 3 suffered significant bulge, but thecell using Example 1 suffered no bulge.

It is understood from FIG. 3 and the observation results that the use ofExample 1 suppresses the electrolytic solution from being decomposed toshow excellent durability as compared to the use of Comparative Example3.

[Oven Test]

Nonaqueous secondary batteries were produced according to theaforementioned manner by using the separator of Example 1 and thepolyethylene microporous membrane of Comparative Example 3. Thebatteries were each charged to 4.2 V. The battery was placed in an oven,and a weight of 5 kg was placed thereon. In this state, the oven was setin such a manner that the temperature of the battery was increased by 2°C. per minute to heat the battery to 200° C. The changes in batteryvoltage are shown in FIG. 4.

It is confirmed from FIG. 4 that Example 1 suffers substantially nochange in battery voltage even on exposing to a high temperature, butComparative Example 3 suffers quick decrease in battery voltage around150° C. It is understood from the above that Example 1 is difficult tocause short circuit even on exposing to a high temperature and isexcellent in mechanical strength at a high temperature as compared toComparative Example 3.

[DSC Analysis]

The separator of Example 1 was analyzed with DSC (differential scanningcalorimetry). DSC2920, produced by TA Instruments Japan Co., Ltd., wasused as a measuring apparatus. A measurement specimen was produced byweighing 5.5 mg of the separator of Example 1 and crimped in an aluminumpan. The measurement was performed in a nitrogen gas atmosphere at atemperature increasing rate of 5° C. per minute and a temperature rangeof 30 to 350° C. The measurement results are shown in FIG. 5.

In FIG. 5, an endothermic peak corresponding to melting of polyethylenewas observed at 110 to 160° C., and a large endothermic peakcorresponding to dehydration reaction of aluminum hydroxide was observedat 250 to 320° C. It is understood from the above that in Example 1, thepolyethylene microporous membrane is melted to cause shutdown, and thenupon exposing to a high temperature, aluminum hydroxide undergoesdehydration reaction associated with large endothermic reaction. It isalso understood from the phenomenon that the separator of the inventionis excellent in flame retardancy.

3. Studies on Particle Size Distribution of Inorganic Filler

The influence of the particle size distribution of the inorganic fillerwas studied by changing the particle size distribution of the inorganicfiller.

Example 4

160.5 g of isophthalic acid chloride was dissolved in 1,120 mL oftetrahydrofuran, to which a solution obtained by dissolving 85.2 g ofm-phenylenediamine in 1,120 mL of tetrahydrofuran was gradually added inthe form of thin flow under stirring, thereby providing a white turbidmilky white solution. After continuing the stirring for approximately 5minutes, an aqueous solution obtained by dissolving 167.6 g of sodiumcarbonate and 317 g of sodium chloride in 3,400 mL of water was quicklyadded thereto under stirring, followed by further stirring for 5minutes. The reaction system was increased in viscosity after severalseconds and then decreased in viscosity, thereby providing a whitesuspension liquid. After allowing to stand the suspension liquid, atransparent aqueous solution layer thus separated was removed, and 185.3g of white polymer of poly-m-phenylene isophthalamide was obtained byfiltration.

The poly-m-phenylene isophthalamide thus obtained in the aforementionedmanner and an inorganic filler containing aluminum hydroxide (H-43M,produced by Showa Denko K. K.) were mixed at a weight ratio of 25/75,and mixed in a concentration of poly-m-phenylene isophthalamide of 5.5%by weight with a mixed solvent containing dimethylacetamide (DMAc) andtripropylene glycol (TPG) at a weight ratio of 50/50, thereby providinga coating slurry. The particle size distribution of the inorganic fillerwas d90 of 1.05, d50 of 0.75 and d10 of 0.38.

A polyethylene microporous membrane used was one produced in the samemanner as in Example 1. A separator for a nonaqueous secondary batteryof the invention was produced in the same manner as in Example 1 exceptthat the aforementioned coating slurry was used. The resulting separatorwas analyzed, and the evaluation results for sliding property andcoating property are shown in Table 2.

Example 5

A separator for a nonaqueous secondary battery of the invention wasproduced in the same manner as in Example 4 except that the inorganicfiller was changed to aluminum hydroxide (H-42M, produced by Showa DenkoK.K.) having a particle size distribution of d90 of 1.07, d50 of 1.02and d10 of 0.50 by laser diffraction. The resulting separator wasanalyzed, and the results are shown in Table 2.

Example 6

A separator for a nonaqueous secondary battery of the invention wasproduced in the same manner as in Example 4 except that the inorganicfiller was changed to aluminum hydroxide (H-32, produced by Showa DenkoK.K.) having a particle size distribution of d90 of 22.0, d50 of 8.0 andd10 of 1.50 by laser diffraction. The resulting separator was analyzed,and the results are shown in Table 2.

Example 7

A separator for a nonaqueous secondary battery of the invention wasproduced in the same manner as in Example 4 except that the inorganicfiller was changed to aluminum hydroxide (H-21, produced by Showa DenkoK.K.) having a particle size distribution of d90 of 58.0, d50 of 23.0and d10 of 5.10 by laser diffraction. The resulting separator wasanalyzed, and the results are shown in Table 2.

TABLE 2 Sliding Coating d10 d50 d90 α property property Example 4 0.380.75 1.05 0.89 good good Example 5 0.50 1.02 1.07 0.56 good good Example6 1.50 8.0 22.0 2.56 good poor Example 7 5.10 23.0 58.0 2.30 good poor

It is understood from the results in Table 2 that Examples 4 and 5 areexcellent in both sliding property and coating property, but Examples 6and 7 are inferior in coating property. It is understood from the abovethat the inorganic filler preferably has 0.1≦d50≦1 (μm) and 0<α≦2. WhileExamples 6 and 7 are inferior in coating property, they suffer noadverse influence upon applying practically to a battery, but have heatresistance, shutdown characteristics, flame retardancy and handlingproperty that are equivalent to Example 1, thereby attainingsufficiently the objects of the invention.

4. Studies on Molecular Weight and the Like of Heat Resistant Resin

The effect of the molecular weight and the like of the heat resistantresin was studied.

Example 8

160.5 g of isophthalic acid chloride was dissolved in 1,120 mL oftetrahydrofuran, to which a solution obtained by dissolving 85.2 g ofm-phenylenediamine in 1,120 mL of tetrahydrofuran was gradually added inthe form of thin flow under stirring, thereby providing a white turbidmilky white solution. After continuing the stirring for approximately 5minutes, an aqueous solution obtained by dissolving 167.6 g of sodiumcarbonate and 317 g of sodium chloride in 3,400 mL of water was quicklyadded thereto under stirring, followed by further stirring for 5minutes. The reaction system was increased in viscosity after severalseconds and then decreased in viscosity, thereby providing a whitesuspension liquid. After allowing to stand the suspension liquid, atransparent aqueous solution layer thus separated was removed, and 185.3g of white polymer of poly-m-phenylene isophthalamide was obtained byfiltration. The polymer had a molecular weight distribution Mw/Mn of 6,a weight average molecular weight Mw of 1.5×10⁵ and a content of a lowmolecular weight matter having a molecular weight of 8,000 or less of3.4% by weight.

A separator for a nonaqueous secondary battery of the invention wasproduced in the same manner as in Example 1 except that thepoly-m-phenylene isophthalamide obtained above was used. The propertiesof the separator were a porosity of the heat resistant porous layer of70%, an air permeability of 310 sec/100 cc, a membrane resistance of 2.8ohm·cm² and a total thickness of 20 μm.

Example 9

185.0 g of white polymer of poly-m-phenylene isophthalamide was obtainedin the same manner as in Example 8 except that a solution obtained bydissolving 160.5 g of isophthalic acid chloride in 1,120 mL oftetrahydrofuran and a solution obtained by dissolving 83.9 g ofm-phenylenediamine in 1,120 mL of tetrahydrofuran were used. Thepoly-m-phenylene isophthalamide had a molecular weight distributionMw/Mn of 10, a weight average molecular weight Mw of 2.0×10⁵ and acontent of a low molecular weight matter having a molecular weight of8,000 or less of 3.0% by weight.

A separator for a nonaqueous secondary battery of the invention wasproduced in the same manner as in Example 1 except that thepoly-m-phenylene isophthalamide obtained above was used. The propertiesof the separator were a porosity of the heat resistant porous layer of65%, an air permeability of 320 sec/100 cc, a membrane resistance of 3.0ohm·cm² and a total thickness of 20 μm.

Example 10

753 g of NMP having a water fraction of 100 ppm or less was placed in areactor equipped with a thermometer, a stirring device and a rawmaterial charging port, and 85.5 g of m-phenylenediamine was dissolvedin NMP, followed by cooling to 0° C. 160.5 g of isophthalic acidchloride was gradually added to the cooled diamine solution understirring to perform reaction. The temperature of the solution wasincreased to 70° C. through the reaction. After terminating theviscosity change, 58.4 g of calcium hydroxide in a powder form was addedthereto, and the reaction was completed by stirring for further 40minutes. The polymerization solution was taken out and reprecipitated inwater to provide 184.0 g of poly-m-phenylene isophthalamide. The polymerhad a molecular weight distribution Mw/Mn of 4, a weight averagemolecular weight Mw of 1.0×10⁵ and a content of a low molecular weightmatter having a molecular weight of 8,000 or less of 0.8% by weight.

A separator for a nonaqueous secondary battery of the invention wasproduced in the same manner as in Example 1 except that thepoly-m-phenylene isophthalamide obtained above was used. The propertiesof the separator were a porosity of the heat resistant porous layer of70%, an air permeability of 400 sec/100 cc, a membrane resistance of 4.9ohm·cm² and an average thickness of 20 μm.

The aforementioned results are summarized in Table 3. The compositeseparators of Examples 8 to 10 were subjected to GPC measurement ofpoly-m-phenylene isophthalamide, and as a result, the molecular weightdistribution Mw/Mn and the weight average molecular weight Mw wereequivalent to the polymers before coating.

TABLE 3 Content of low molecular Porosity of heat Air Membrane weightmatter resistant layer permeability resistance Mw/Mn Mw (×10⁵) (% byweight) (%) (sec/100 cc) (ohm · cm²) Example 8 6 1.5 3.4 70 310 2.8Example 9 10 2.0 3 65 320 3.0 Example 10 4 1.0 0.8 70 400 4.9

It is understood from the results in Table 3 that the separators ofExamples 8 and 9 are excellent in air permeability and membraneresistance as compared to the separator of Example 10. It is understoodfrom the above that it is preferred to use a polymer having a molecularweight distribution Mw/Mn satisfying 5≦Mw/Mn≦100 and a weight averagemolecular weight Mw of 8.0×10³ to 1.0×10⁶, or to use a polymercontaining a low molecular weight polymer having a molecular weight of8,000 or less in an amount of 1 to 15% by weight. While Example 10 isinferior in air permeability and membrane resistance, it suffers noproblem in practical use, but has heat resistance, shutdowncharacteristics, flame retardancy and handling property that areequivalent to Example 1, thereby attaining sufficiently the objects ofthe invention.

5. Studies on End Group Concentration Ratio of Polyamide

The effect of the end group concentration ratio of the wholly aromaticpolyamide was studied.

Example 11

160.5 g of isophthalic acid chloride was dissolved in 1,120 mL oftetrahydrofuran, to which a solution obtained by dissolving 84.9 g ofm-phenylenediamine in 1,120 mL of tetrahydrofuran was gradually added inthe form of thin flow under stirring, thereby providing a white turbidmilky white solution. After continuing the stirring for approximately 5minutes, an aqueous solution obtained by dissolving 167.6 g of sodiumcarbonate and 317 g of sodium chloride in 3,400 mL of water was quicklyadded thereto under stirring, followed by further stirring for 5minutes. The reaction system was increased in viscosity after severalseconds and then decreased in viscosity, thereby providing a whitesuspension liquid. After allowing to stand the suspension liquid, atransparent aqueous solution layer thus separated was removed, and 185.3g of white polymer of poly-m-phenylene isophthalamide was obtained byfiltration. The polyamide had an end group concentration ratio[COOX]/[NH₂] of 2.2. A separator for a nonaqueous secondary battery ofthe invention was produced in the same manner as in Example 1 exceptthat the poly-m-phenylene isophthalamide obtained above was used.

A button battery was produced by using the aforementioned separator inthe following manner.

89.5 parts by weight of powder of lithium cobaltate (LiCoO₂, produced byNippon Chemical Industrial Co., Ltd.), 4.5 parts by weight of acetyleneblack and a 6% by weight NMP solution of PVdF providing 6 parts byweight of PVdF in terms of dry weights were used to prepare a positiveelectrode paste. The resulting paste was coated on an aluminum foilhaving a thickness of 20 μm, and dried, followed by pressing, to providea positive electrode having a thickness of 97 μm.

87 parts by weight of powder of mesophase carbon microbeads (MCMB,produced by Osaka Gas Chemicals Co., Ltd.), 3 parts by weight ofacetylene black and a 6% by weight NMP solution of PVdF providing 10parts by weight of PVdF in terms of dry weights were used to prepare anegative electrode paste. The resulting paste was coated on a copperfoil having a thickness of 18 μm, and dried, followed by pressing, toprovide a negative electrode of 90 μm.

A button battery (CR2032) having a capacity of approximately 4.5 mAh wasproduced by using the separator for a nonaqueous secondary battery, thepositive electrode and the negative electrode mentioned above. Theelectrolytic solution was obtained by dissolving LiPF₆ in aconcentration of 1 M in a solvent containing ethylene carbonate, diethylcarbonate and ethylmethyl carbonate mixed at a weight ratio of 11/2/1.

The button battery thus produced was able to perform charging anddischarging without any problem. After the button battery was subjectedto 100 cycles of constant current and constant voltage charging at 4.2 Vand constant current discharging at 2.75 V, the battery was measured fordischarge capacity, and thus it was found that the battery had favorablecycle characteristics of 4.1 mAh.

Example 12

753 g of NMP having a water fraction of 100 ppm or less was placed in areactor equipped with a thermometer, a stirring device and a rawmaterial charging port, and 84.9 g of m-phenylenediamine was dissolvedin NMP, followed by cooling to 0° C. 160.5 g of isophthalic acidchloride was gradually added to the cooled diamine solution understirring to perform reaction. The temperature of the solution wasincreased to 70° C. through the reaction. After terminating theviscosity change, 58.4 g of calcium hydroxide in a powder form was addedthereto, and the reaction was completed by stirring for further 40minutes. The polymerization solution was taken out and reprecipitated inwater to provide 184.0 g of poly-m-phenylene isophthalamide. Thepolyamide had an end group concentration ratio [COOX]/[NH₂] of 2.1. Aseparator for a nonaqueous secondary battery of the invention wasproduced in the same manner as in Example 1 except that thepoly-m-phenylene isophthalamide obtained above was used.

A button battery was produced in the same manner as in Example 11 exceptthat the resulting separator was used. The button battery thus producedwas able to perform charging and discharging without any problem. Afterthe button battery was subjected to 100 cycles of constant current andconstant voltage charging at 4.2 V and constant current discharging at2.75 V, the battery was measured for discharge capacity, and thus it wasfound that the battery had favorable cycle characteristics of 4.1 mAh.

Example 13

16.4 g of poly-m-phenylene isophthalamide in the form of a white polymerwas obtained in the same manner as in Example 11 except that 86.4 g ofm-phenylenediamine was used. The polyamide had an end groupconcentration ratio [COOX] [NH₂] of 0.8. A separator for a nonaqueoussecondary battery of the invention was produced in the same manner as inExample 1 except that the poly-m-phenylene isophthalamide obtained abovewas used.

A button battery was produced in the same manner as in Example 11 exceptthat the resulting separator was used. The button battery thus producedwas able to perform charging and discharging without any problem. Afterthe button battery was subjected to 100 cycles of constant current andconstant voltage charging at 4.2V and constant current discharging at2.75 V, the battery was measured for discharge capacity, and it was 2.2mAh.

The results are summarized in Table 4.

TABLE 4 Discharge capacity after 100 cycles [COOX]/[NH₂] (mAh) Example11 2.2 4.1 Example 12 2.1 4.1 Example 13 0.8 2.2

It is understood from Table 4 that Examples 11 and 12 are excellent incharging and discharging characteristics as compared to Example 13. Itis understood from the above that, when aromatic polyamide is used asthe heat resistant resin, the end group concentration ratio of thearomatic polyamide is preferably [COOX]/[NH₂]≧1. While Example 13 isslightly inferior in cycle characteristics, it suffers no problem inpractical use, but has heat resistance, shutdown characteristics, flameretardancy and handling property that are equivalent to Example 1,thereby attaining sufficiently the objects of the invention.

INDUSTRIAL APPLICABILITY

The invention is effectively utilized as techniques for enhancingcharacteristics of a nonaqueous secondary battery.

1. A separator for a nonaqueous secondary battery comprising apolyolefin microporous membrane at least one surface of which islaminated with a heat resistant porous layer containing a heat resistantresin, the heat resistant porous layer containing an inorganic fillercontaining a metallic hydroxide that undergoes dehydration reaction at atemperature of 200 to 400° C., wherein the heat resistant resin ismeta-type wholly aromatic polyamide.
 2. The separator for a nonaqueoussecondary battery according to claim 1, characterized in that the heatresistant resin has a molecular weight distribution Mw/Mn of 5≦Mw/Mn≦100and a weight average molecular weight of 8.0×10³ to 1.0×10⁶.
 3. Theseparator for a nonaqueous secondary battery according to claim 1,characterized in that the heat resistant resin contains a low molecularweight polymer having a molecular weight of 8,000 or less in an amountof 1 to 15% by weight.
 4. The separator for a nonaqueous secondarybattery according to claim 1, characterized in that the heat resistantresin is wholly aromatic polyamide, and the wholly aromatic polyamidehas an end group concentration ratio of [COOX]/[NH₂]≧1 (wherein Xrepresents an alkali metal or an alkaline earth metal).
 5. A separatorfor a nonaqueous secondary battery comprising a polyolefin microporousmembrane at least one surface of which is laminated with a heatresistant porous layer containing a heat resistant resin, the heatresistant porous layer containing an inorganic filler containing ametallic hydroxide that undergoes dehydration reaction at a temperatureof 200 to 400° C., wherein the heat resistant porous layer has aporosity of 60 to 90%.
 6. A separator for a nonaqueous secondary batterycomprising a polyolefin microporous membrane at least one surface ofwhich is laminated with a heat resistant porous layer containing a heatresistant resin, the heat resistant porous layer containing an inorganicfiller containing a metallic hydroxide that undergoes dehydrationreaction at a temperature of 200 to 400° C., wherein a coated amount ofthe heat resistant porous layer is 2 to 10 g/m².
 7. A separator for anonaqueous secondary battery comprising a polyolefin microporousmembrane at least one surface of which is laminated with a heatresistant porous layer containing a heat resistant resin, the heatresistant porous layer containing an inorganic filler containing ametallic hydroxide that undergoes dehydration reaction at a temperatureof 200 to 400° C., wherein the separator has an air permeability (JISP8117) of 500 sec/100 cc or less.
 8. A separator for a nonaqueoussecondary battery comprising a polyolefin microporous membrane at leastone surface of which is laminated with a heat resistant porous layercontaining a heat resistant resin, the heat resistant porous layercontaining an inorganic filler containing a metallic hydroxide thatundergoes dehydration reaction at a temperature of 200 to 400° C.,wherein the separator has a membrane resistance of 0.5 to 10 ohm·cm². 9.A separator for a nonaqueous secondary battery comprising a polyolefinmicroporous membrane at least one surface of which is laminated with aheat resistant porous layer containing a heat resistant resin, the heatresistant porous layer containing an inorganic filler containing ametallic hydroxide that undergoes dehydration reaction at a temperatureof 200 to 400° C., wherein the separator has a heat contraction ratio at175° C. of 30% or less in both MD and TD.
 10. A separator for anonaqueous secondary battery comprising a polyolefin microporousmembrane at least one surface of which is laminated with a heatresistant porous layer containing a heat resistant resin, the heatresistant porous layer containing an inorganic filler containing ametallic hydroxide that undergoes dehydration reaction at a temperatureof 200 to 400° C., wherein the inorganic filler is surface-treated witha silane coupling agent.
 11. The separator for a nonaqueous secondarybattery according to claim 1, characterized in that the metallichydroxide is at least one of aluminum hydroxide and magnesium hydroxide.12. The separator for a nonaqueous secondary battery according to claim1, characterized in that the inorganic filler has an average particlediameter of 0.1 to 1 μm.
 13. The separator for a nonaqueous secondarybattery according to claim 1, characterized in that the heat resistantporous layer contains the inorganic filler in an amount of 50 to 95% byweight.
 14. The separator for a nonaqueous secondary battery accordingto claim 5, characterized in that the heat resistant resin is at leastone of wholly aromatic polyamide, polyimide, polyamideimide,polysulfone, polyketone, polyetherketone, polyetherimide and cellulose.15. The separator for a nonaqueous secondary battery according to claim1, characterized in that the separator for a nonaqueous secondarybattery has a thickness of 25 μm or less, the polyolefin microporousmembrane has a thickness of 5 μm or more, and the heat resistant porouslayer has a thickness of 2 μm or more.
 16. The separator for anonaqueous secondary battery according to claim 1, characterized in thatthe heat resistant porous layer is coated on both surfaces of thepolyethylene microporous membrane.
 17. A nonaqueous secondary batterycomprising a positive electrode, a negative electrode, a separatorprovided between the electrodes, and a nonaqueous electrolytic solution,characterized in that the separator is the separator for a nonaqueoussecondary battery according to claim 1.